Dielectric composition, dielectric element, electronic component, and multilayer electronic component

ABSTRACT

A dielectric composition with high voltage resistance and favorable reliability, and an electronic component using the dielectric composition. The dielectric composition contains, as a main component, a tungsten bronze type composite oxide represented by a chemical formula (Sr 1.00-(s+t) Ba s Ca t ) 6.00-x R x (Ti 1.00-a Zr a ) x+2.00 (Nb 1.00-b Ta b ) 8.00-x O 30.00 , in which the R is at least one element selected from Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and s, t, x, a, and b satisfy 0.50≤s≤1.00, 0≤t≤0.30, 0.50≤s+t≤1.00, 1.50&lt;x≤3.00, 0.20≤a≤1.00, and 0≤b≤1.00. At least one selected from Mn, Mg, Co, V, W, Mo, Si, Li, B, and Al is contained as a sub component in 0.10 mol or more and 20.00 mol or less with respect to 100 mol of the main component.

TECHNICAL FIELD

The present invention relates to a dielectric composition, a dielectricelement, an electronic component, and a multilayer electronic componentwhich are suitably used particularly under a high-temperatureenvironment such as in-vehicle use.

BACKGROUND ART

For example, a multilayer ceramic capacitor is used in a variety ofelectronic equipment because of high reliability and low cost thereof.Specifically, the multilayer ceramic capacitor is used in informationterminals, home electronics, automobile electronic components, and thelike. In these use applications, particularly, in a multilayer ceramiccapacitor for use application of in-vehicle use or the like, as comparedto a typical multilayer ceramic capacitor, securement up to ahigher-temperature region is required in some cases and higherreliability is necessary. It is necessary that the multilayer ceramiccapacitor is not broken against a voltage to be applied, that is, hashigh voltage resistance. Further, since a high AC voltage is applied toa resonant capacitor used in a non-contact power supply resonant circuitor the like, the resonant capacitor is required to have high AC voltageresistance as well as high DC voltage resistance.

Patent document 1 discloses a technology relating to a tungsten bronzetype composite oxide exhibiting a high specific permittivity and highspecific resistance.

However, in the patent document 1, an alkali metal element is containedas a constituent element of a main component. Since the alkali metalelement has high volatility, there is a problem in that handling at thetime of manufacturing is prone to be cumbersome, for example, a processof filling an alkali metal element needs to be introduced in processes.

Further, since a lattice defect caused by potassium with high volatilityeasily occurs in the dielectric composition and thus a conductionelectron is easily generated, there is a problem in that high DC voltageresistance is difficult to obtain.

Further, patent document 2 discloses a technology relating to aperovskite type oxide having high DC voltage resistance at 150° C.

However, since the perovskite type oxide has a low specific permittivityin a high-temperature region of 175° C. or higher that is expected to beused hereafter, there is a problem in that a desired capacitance isdifficult to obtain.

Further, non-patent document 1 discloses a technology relating to atungsten bronze type dielectric Ba₂MTi₂Nb₃O₁₅ (M=Bi³⁺, La³⁺, Nd³⁺, Sm³⁺,Gd³⁺) with a high specific permittivity and a low dielectric loss. Thetungsten bronze type dielectric has a high specific permittivity at roomtemperature of about 100 to 700 and a favorable value of tan δ at roomtemperature of 5% or less. In addition, non-patent document 2 disclosesa technology relating to a tungsten bronze type dielectricBa₂Sm₂Ti₄Ta₆O₃₀ with a high specific permittivity and a low dielectricloss. The tungsten bronze type dielectric has a high specificpermittivity at room temperature of about 120 and a favorable value oftan6 at room temperature of 3% or less.

Further, regarding AC voltage resistance, patent document 3 discloses atechnology of improving AC voltage resistance using a dielectric ceramiccomposition containing a compound represented by a composition formulaBa_(x)(Ti_(1-y)Sn_(y))O₃ and an oxide of Zn. By strictly controlling thecomposition of the dielectric ceramic composition, a high specificpermittivity, a low dielectric loss, and high AC voltage resistance arerealized.

However, any of the patent documents and the non-patent documents do notmention dielectric properties, DC voltage resistance, and AC voltageresistance which are secured up to a high-temperature region of 175° C.or higher that is expected to be used hereafter. Further, in the patentdocument 3, since the invention is based on the assumption of asingle-plate capacitor of about 1 mm, there is a problem in thatnecessary AC voltage resistance is not obtainable in a region in whichthe thickness of the dielectric layer is 10 μm or less like themultilayer ceramic capacitor. In particular, the magnitude of DC voltageresistance or AC voltage resistance is a property that is essential in amultilayer ceramic capacitor used for in-vehicle use, a non-contactpower supply, or the like, and this is increasingly required with highbreakdown voltage of an in-vehicle module in recent years.

CITATION LIST Patent Document

Patent document 1: WO 2006/114914 A

Patent document 2: JP 11-224827 A

Patent document 3: JP 2014-1131 A

Non-Patent Document

Non-patent document 1: JOURNAL OF APPLIED PHYSICS 101, 104114 (2007)“Dielectric and structural studies of Ba₂MTi₂Nb₃O₁₅ (BMTNO₁₅, M=Bi³⁺,La³⁺, Nd³⁺, Sm³⁺, Gd³⁺) tetragonal tungsten bronze-structured ceramics”

Non-patent document 2: Journal of the American Ceramic Society, 93[3]782-786 (2010) “Crystal structure and ferroelectric behaviors ofBa₅SmTi₃Ta₇O₃₀ and Ba₄Sm₂Ti₄Ta₆O₃₀ tungsten bronze ceramics”

SUMMARY OF THE INVENTION Problem to be Solved by the Invention

The present invention is made in view of the above-described problems,and aims to provide a dielectric composition which is suitably usedunder a high-temperature environment such as in-vehicle use, and hashigh AC voltage resistance and a low dielectric loss as well as high DCvoltage resistance and high specific resistance even under an usageenvironment of 175° C. or higher, and a dielectric element, anelectronic component, and a multilayer electronic component which usethe dielectric composition.

Means for Solving Problem

In order to achieve the object, a dielectric composition of the presentinvention contains, as a main component,

a tungsten bronze type composite oxide represented by a chemical formula(Sr_(1.00-(s+t))Ba_(s)Ca_(t))_(6.00-x)R_(x)(Ti_(1.00-a)Zr_(a))_(x+2.00)(Nb_(1.00-b)Ta_(b))_(8.00-x)O_(30.00),

in which the R is at least one element selected from Y, La, Pr, Nd, Sm,Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and

s, t, x, a, and b satisfy

0.50≤s≤1.00,

0≤t≤0.30,

0.50≤s+t≤1.00,

1.50<x≤3.00,

0.20≤a≤1.00, and

0≤b≤1.00.

With the above-described dielectric composition, it is possible toobtain a dielectric composition which is suitably used under ahigh-temperature environment and has high AC voltage resistance and alow dielectric loss as well as high DC voltage resistance and highspecific resistance.

Further, as a desirable embodiment of the present invention, at leastone selected from Mn, Mg, Co, V, W, Mo, Si, Li, B, and Al is containedas a sub component in 0.10 mol or more and 20.00 mol or less withrespect to 100 mol of the main component. Accordingly, a low dielectricloss is obtained in addition to higher specific resistance, higher DCvoltage resistance, and higher AC voltage resistance.

As a desirable embodiment of the present invention, a substitutionamount a of Zr contained in the main component is preferably0.50≤a≤1.00. Accordingly, it is possible not only to obtain higher DCvoltage resistance but also to obtain higher AC voltage resistance and alower dielectric loss.

A dielectric element according to the present invention preferablyincludes the above-described dielectric composition.

When the dielectric element according to the present invention includesthe above-described dielectric composition, the dielectric element canbe used under a high-temperature environment such as in-vehicle use.

An electronic component according to the present invention preferablyincludes a dielectric layer formed by the above-described dielectriccomposition.

A multilayer electronic component according to the present inventionpreferably includes a multilayer portion obtained by alternatelystacking a dielectric layer formed by the above-described dielectriccomposition and an internal electrode layer.

When the electronic component and the multilayer electronic componentaccording to the present invention include a dielectric layer formed bythe above-described dielectric composition, the electronic component andthe multilayer electronic component can be used under a high-temperatureenvironment such as in-vehicle use.

The use application of the electronic component having a dielectriclayer formed by the dielectric composition according to the presentinvention is not particularly limited, but the electronic component isuseful for a multilayer ceramic capacitor, a piezoelectric element, achip varistor, a chip thermistor, and the like.

EFFECT OF THE INVENTION

The present invention can provide a dielectric composition which issuitably used under a high-temperature environment such as in-vehicleuse, and has high AC voltage resistance and a low dielectric loss aswell as high DC voltage resistance and high specific resistance evenunder an usage environment of 175° C. or higher, and a dielectricelement, an electronic component, and a multilayer electronic componentwhich use the dielectric composition.

BRIEF DESCRIPTION OF DRAWINGS

FIGURE illustrates a cross-sectional view of a multilayer ceramiccapacitor according to an embodiment of the present invention.

MODE(S) FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described.

A dielectric composition according to the present embodiment contains,as a main component,

a tungsten bronze type composite oxide represented by a chemical formula(Sr_(1.00-(s+t))Ba_(s)Ca_(t))_(6.00-x)R_(x)(Ti_(1.00-a)Zr_(a))_(x+2.00)(Nb_(1.00-b)Ta_(b))_(8.00-x)O_(30.00),

in which the R is at least one element selected from Y, La, Pr, Nd, Sm,Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and

s, t, x, a, and b satisfy

0.50≤s≤1.00,

0≤t≤0.30,

0.50≤s+t≤1.00,

1.50<x≤3.00,

0.20≤a≤1.00, and

0≤b≤1.00.

When the dielectric composition according to the present embodimentcontains, as a main component, a tungsten bronze type composite oxiderepresented by the chemical formula, high DC voltage resistance iseasily obtained. Regarding the reason for this, the present inventorsconsider as follows. Since the tungsten bronze type composite oxide asthe main component of the present embodiment has a characteristic thatthe bandgap is wide, electrons in the valence band are difficult toexcite to the conduction band so that a carrier concentration ofelectrons that are a majority carrier involved in conduction can besuppressed. In addition, it is considered that the carrier concentrationof conduction electrons that are a majority carrier affects electronavalanche that is a typical breakdown mode of the DC voltage resistance.In the dielectric composition of the present invention, since thecarrier concentration of electrons that are a majority carrier can besuppressed to be low, it is considered that breakdown caused by electronavalanche is difficult to occur. Further, since the bandgap is wide, acertain degree of width of the bandgap can be maintained even when highfield strength is applied. According to this, it is considered that highDC voltage resistance is easily obtained even in a high electric field.In addition, since an alkali metal with high volatility is notcontained, a lattice defect is difficult to occur and conductionelectrons are difficult to generate so that the dielectric compositionof the present invention has a characteristic that the specificresistance and the DC voltage resistance are high.

When s and t in the chemical formula are 0.50≤s≤1.00, 0≤t≤0.30, and0.50≤s+t≤1.00, high DC voltage resistance and a low dielectric loss areeasily obtained even under a high-temperature environment of 200° C. Onthe other hand, in a case where K, Na, or the like that is an alkalimetal element is contained in addition to Sr, Ba, and Ca, sincevolatility of these alkali metal elements is high, a lattice defecteasily occur by a heat treatment (such as firing process), and as aresult, there is a tendency that high DC voltage resistance is difficultto obtain. In addition, t represents a substitution amount of Ca. Ca isan arbitrary component and an upper limit of the substitution amountthereof is 0.30.

When R in the chemical formula is at least one element selected from Y,La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, high DC voltageresistance is easily obtained.

When a tungsten bronze type composite oxide in which x in the chemicalformula is 1.50<x≤3.00, for example, which is represented by(Sr_(1.00-(s+t))Ba_(s)Ca_(t))_(4.00)R_(2.00)(Ti_(1.00-a)Zr_(a))_(4.00)(Nb_(1.00-b)Ta_(b))_(6.00)O_(30.00)in the case of x=2,(Sr_(1.00-(s+t))Ba_(s)Ca_(t))_(3.00)R_(3.00)(Ti_(1.00-a)Zr_(a))_(5.00)(Nb_(1.00-b)Ta_(b))_(5.00)O_(30.00)in the case of x=3, or the like is used as the main component, high ACvoltage resistance and a low dielectric loss are easily obtained. Thereason for this is considered that when rare earth is contained at acertain ratio or more in the main component of the tungsten bronze typecomposite oxide, bond strength between elements in the crystal, or thelike changes to affect the dielectric loss. Further, it is consideredthat since the tungsten bronze type composite oxide of the chemicalformula has a low dielectric loss in addition to a high bandgap, thefollowability of ion displacement with respect to the alternatingelectric field also becomes favorable and the AC voltage resistancebecomes high.

On the other hand, in a case where x is more than 3.00, for example, ina composite oxide of a chemical formula Ba₂La₄Zr₆Nb₄O₃₀, or the like,the crystal structure of the tungsten bronze type is difficult to formso that it is difficult to obtain high AC voltage resistance that is afeature of the present invention.

When a substitution amount a of Zr in the chemical formula is0.20≤a≤1.00, the bandgap is widened, and thus high DC voltage resistanceand a low dielectric loss are easily obtained.

Further, when the substitution amount a of Zr in the chemical formula is0.50≤a≤1.00, the bandgap is further widened, and thus high DC voltageresistance is easily obtained.

Ta in the chemical formula is an arbitrary component, and also in acomposite oxide in which Nb is substituted with Ta, the crystalstructure of the tungsten bronze type can be maintained. Thesubstitution amount of Ta is preferably 0.10≤b≤1.00, and accordingly,higher DC voltage resistance is easily obtained.

As the sub component, it is preferable that at least one or moreelements selected from Mn, Mg, Co, V, W, Mo, Si, Li, B, and Al arecontained. Owing to an interaction between Zr contained in the maincomponent and these elements, high DC voltage resistance and highspecific resistance are easily obtained. Preferably, when thesubstitution amount a of Zr is 0.80≤a≤1.00, the interaction is enhancedso that higher DC voltage resistance is easily obtained.

Further, when the amount of the sub component is set to 0.10 mol or moreand 20.00 mol or less with respect to 100 mol of the main component, alow dielectric loss of less than 0.20% can be obtained at 200° C. inaddition to high specific resistance of 9.00×10¹² Ω/cm or more at 200°C. Moreover, higher DC voltage resistance can be obtained even at a hightemperature of 175° C. or higher.

Further, other than R contained in the main component, at least oneelement selected from Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,and Lu may be contained as a second sub component. The second subcomponent is an arbitrary component and an upper limit of the amountthereof is determined in a range within which the object of theinvention can be achieved.

Incidentally, the dielectric composition may further contain fineimpurities or other sub components as long as they do not largelydeteriorate dielectric properties that are the effects of the presentinvention, that is, the specific permittivity, the specific resistance,the DC voltage resistance, and the AC voltage resistance. Therefore, theamount of the main component is not particularly limited, and forexample, is 50 mol % or more and 100 mol% or less with respect to thewhole dielectric composition containing the main component.

Next, description will be given using a multilayer ceramic capacitor asan example. Figure illustrates a multilayer ceramic capacitor accordingto an embodiment of the present invention. A multilayer ceramiccapacitor 1 has a capacitor element main body 10 having a configurationin which a dielectric layer 2 and an internal electrode layer 3 arealternately stacked. A pair of external electrodes 4, which isconductive with each of the internal electrode layers 3 alternatelydisposed inside the element main body 10, is formed at both ends of thecapacitor element main body 10. The shape of the capacitor element mainbody 10 is not particularly limited, and is typically a rectangularparallelepiped shape. In addition, the dimension thereof is also notparticularly limited, and the dimension may be appropriately determineddepending on the use application.

The thickness of the dielectric layer 2 is not particularly limited, andmay be appropriately determined depending on the use application of themultilayer ceramic capacitor 1.

The conductive material contained in the internal electrode layer 3 isnot particularly limited, and is preferably Ni, Pd, Ag, a Pd-Ag alloy,Cu, or a Cu-based alloy. Incidentally, a trace amount of variouscomponents such as P may be contained in about 0.1% by weight or less inNi, Pd, Ag, a Pd—Ag alloy, Cu, or a Cu-based alloy. In addition, theinternal electrode layer 3 may be formed using a commercially availablepaste for an electrode. The thickness of the internal electrode layer 3may be appropriately determined depending on the use application or thelike.

The conductive material contained in the external electrode 4 is notparticularly limited, and Cu, a Cu-based alloy, Ni, a Ni-based alloy,Ag, an Ag—Pd alloy, and the like are typically used. The thickness ofthe external electrode may be appropriately determined depending on theuse application or the like, and typically, is preferably about 5 μm to50 μm. As necessary, a coating layer is formed on the surface of theexternal electrode by plating or the like.

Next, an example of a method for manufacturing the multilayer ceramiccapacitor illustrated in FIGURE will be described.

The multilayer ceramic capacitor 1 of the present embodiment ismanufactured by producing a green chip by a typical printing method orsheet method using a paste, firing the green chip, then applying anexternal electrode to the green chip, and firing the obtained product,similarly to a multilayer ceramic capacitor of the related art.Hereinafter, the manufacturing method will be described in detail.

An example of the method for manufacturing the multilayer ceramiccapacitor according to the present embodiment will be described.

First, raw materials are prepared such that the main component has adesired proportion, and are mixed and heat-treated (calcined) at 800° C.or higher. Thus, calcined powder can be obtained. Preferably, a heattreatment is performed at 800° C. to 1000° C. such that the particlesize of the calcined powder is 0.1 μm or more and 5.0 μm or less. It ispreferable that a different phase such as Ba₅Nb₄O₁₅ having ananisotropic shape is not contained in the calcined powder.

Regarding the raw materials, an oxide mainly configured by Sr, Ba, Ca,Ti, Zr, Nb, Ta, Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, orLu, or a mixture thereof can be used as raw material powder. Moreover,the raw materials can be appropriately selected from various compoundsthat become the aforementioned oxide or composite oxide by firing, forexample, carbonate, oxalate, nitrate, hydroxide, an organometalliccompound, and the like and can be mixed for use. Specifically, SrO orSrCO₃ may be used as a raw material of Sr.

Further, in a case where the dielectric composition according to thepresent embodiment contains a sub component, a raw material of the subcomponent is also prepared. The raw material of the sub component is notparticularly limited, and oxides of respective components or mixturesthereof can be used as raw material powder. Moreover, the raw materialscan be appropriately selected from various compounds that become theaforementioned oxide or composite oxide by firing, for example,carbonate, oxalate, nitrate, hydroxide, an organometallic compound, andthe like and can be mixed for use. Specifically, MgO or MgCO₃ may beused as a raw material of Mg.

The prepared calcined powder of the main components and the raw materialof the sub component are weighed to have a predetermined compositionalratio and mixed, thereby obtaining a dielectric composition rawmaterial. Examples of a mixing method include wet mixing performed usinga ball mill and dry mixing performed using a dry mixer.

This dielectric composition raw material is prepared in the form of acoating material to prepare a paste for a dielectric layer. The pastefor a dielectric layer may be an organic coating material obtained bykneading a dielectric raw material and an organic vehicle or may be anaqueous coating material.

The organic vehicle is obtained by dissolving a binder in an organicsolvent. The binder used in the organic vehicle is not particularlylimited, and may be appropriately selected from typical various binderssuch as ethylcellulose and polyvinyl butyral. The organic solvent to beused is also not particularly limited, and may be appropriately selectedfrom various organic solvents such as terpineol, butyl carbitol, andacetone depending on a method to be used such as a printing method or asheet method.

Further, in a case where the paste for a dielectric layer is produced inthe form of an aqueous coating material, an aqueous vehicle obtained bydissolving a water-soluble binder, a dispersant, or the like in waterand a dielectric raw material may be kneaded. The water-soluble binderused in the aqueous vehicle is not particularly limited, and forexample, polyvinyl alcohol, cellulose, a water-soluble acrylic resin,and the like may be used.

A paste for an internal electrode layer is prepared by kneading theabove-described organic vehicle with conductive materials formed fromvarious conductive metals or alloys described above, various oxides,which become the above-described conductive material after firing, anorganometallic compound, resinate, and the like.

A paste for an external electrode may be prepared in the similar mannerto the paste for an internal electrode layer described above.

The amount of the organic vehicle in each paste described above is notparticularly limited, and may be a typical amount, for example, theamount of the binder may be about 1% by weight to 5% by weight and theamount of the solvent may be about 10% by weight to 50% by weight. Inaddition, additives selected from various dispersants, plasticizers,dielectric materials, insulator materials, and the like may be containedin each paste as necessary. The total amount of these additives is setto preferably 10% by weight or less.

In the case of using a printing method, the paste for a dielectric layerand the paste for an internal electrode layer are printed on a substratesuch as PET, stacked, cut in a predetermined shape, and then peeled offfrom the substrate to obtain a green chip.

Further, in the case of using a sheet method, a green sheet is formedusing the paste for a dielectric layer, the paste for an internalelectrode layer is printed on the green sheet, and then these arestacked to obtain a green chip.

The green chip is subjected to a binder removal treatment before firingdescribed later. As binder removal conditions, a temperature increaserate is set to preferably 5° C./hr to 300° C./hr, a retentiontemperature is set to preferably 180° C. to 500° C., and a temperatureretention time is set to preferably 0.5 hours to 24 hours. In addition,the atmosphere of the binder removal treatment is set to air orreductive atmosphere.

Further, the retention temperature at the time of firing is preferably1000° C. to 1400° C. and more preferably 1100° C. to 1360° C. When theretention temperature is less than the above ranges, densification isnot sufficient. When the retention temperature exceeds the above ranges,disconnection of the electrode by abnormal sintering of the internalelectrode layer and deterioration in capacity change ratio by diffusionof an internal electrode layer constituent material easily occur. Inaddition, when the retention temperature exceeds the above ranges, thereis a concern that dielectric particles coarsen to decrease DC voltageresistance.

As firing conditions other than the above firing conditions, in order toachieve uniform firing of a chip, the temperature increase rate is setto preferably 50° C./hr to 500° C./hr and more preferably 200° C./hr to300° C./hr, and in order to control the particle diameter distributionafter sintering within a range of 0.1 μm to 10.0 μm, the temperatureretention time is set to preferably 0.5 hours to 24 hours and morepreferably 1 hour to 3 hours, and the cooling rate is set to preferably50° C./hr to 500° C./hr and more preferably 200° C./hr to 300° C./hr.

In the above-described binder removal treatment, for example, a wetteror the like may be used in wetting of N₂ gas, mixed gas, or the like. Inthis case, the water temperature is preferably about 5° C. to 75° C. Inaddition, the binder removal treatment, firing, and annealing may beperformed consecutively or independently.

The capacitor element main body 10 obtained as described above ispolished at the end faces thereof, for example, by barrel polishing,sandblasting, or the like and the paste for an external electrode isapplied and fired, thereby forming the external electrode 4. Then, asnecessary, a coating layer is formed on the surface of the externalelectrode 4 by plating or the like.

Hereinbefore, the embodiments of the present invention have beendescribed. The present invention is not limited to the aforementionedembodiments, and can be variously modified in a range not departing fromthe gist of the present invention.

EXAMPLES

Hereinafter, the present invention will be described in more detail bymeans of specific examples of the present invention. The presentinvention is not limited to these examples. Incidentally, specimensmarked with × in Table 2 are outside the range of the present invention.

As a raw material of the main component, each powder of SrCO₃, BaCO₃,CaCO₃, TiO₂, ZrO₂, Nb₂O₅, Ta₂O₅, Bi₂O₃, Y₂O₃, La₂O₃, Pr₂O₃, Nd₂O₃,Sm₂O₃, Eu₂O₃, Gd₂O₃, Tb₂O₃, Dy₂O₃, Ho₂O₃, Er₂O₃, Tm₂O₃, Yb₂O₃, and Lu₂O₃was prepared.

These materials were weighed to have the main component composition inTable 1, then wet-mixed with a ball mill, dried, and calcined at 800° C.to obtain calcined powder of the main component. A dielectriccomposition raw material was prepared. As a raw material of the subcomponent, each powder of SiO₂, MgO, Co₂O₃, V₂O₅, WO₃, MoO₃, MnO, SiO₂,Li₂CO₃, B₂O₃, Al₂O₃, and Fe₃O₄ was prepared and the main components andthe sub components were mixed to respectively have a proportion in Table1 to obtain dielectric composition raw materials of Specimen No. 1 toSpecimen No. 65.

TABLE 1 Accessory component [mol %] 1.00 − (with respect to 100 mol ofmain component) (s + t) s t Re x a b Mg Si Co V W Mo Mn Li B Al FeSpecimen 0.00 1.00 0.00 La 2.00 0.30 0.00 — — — — — — — — — — — No. 1Specimen 0.30 0.70 0.00 La 2.00 0.30 0.00 — — — — — — — — — — — No. 2Specimen 0.50 0.50 0.00 La 2.00 0.30 0.00 — — — — — — — — — — — No. 3Specimen 0.00 0.70 0.30 La 2.00 0.30 0.00 — — — — — — — — — — — No. 4Specimen 0.20 0.50 0.30 La 2.00 0.30 0.00 — — — — — — — — — — — No. 5※Specimen 0.30 0.40 0.30 La 2.00 0.30 0.00 — — — — — — — — — — — No. 6※Specimen 0.10 0.50 0.40 La 2.00 0.30 0.00 — — — — — — — — — — — No. 7※Specimen 0.00 0.50 0.50 La 2.00 0.30 0.00 — — — — — — — — — — — No. 8※Specimen 0.00 1.00 0.00 La 1.00 0.30 0.00 — — — — — — — — — — — No. 9Specimen 0.00 1.00 0.00 La 1.55 0.30 0.00 — — — — — — — — — — — No. 10Specimen 0.00 1.00 0.00 La 2.50 0.30 0.00 — — — — — — — — — — — No. 11Specimen 0.00 1.00 0.00 La 3.00 0.30 0.00 — — — — — — — — — — — No. 12※Specimen 0.00 1.00 0.00 La 4.00 0.30 0.00 — — — — — — — — — — — No. 13Specimen 0.00 1.00 0.00 Y 2.00 0.30 0.00 — — — — — — — — — — — No. 14Specimen 0.00 1.00 0.00 Pr 2.00 0.30 0.00 — — — — — — — — — — — No. 15Specimen 0.00 1.00 0.00 Nd 2.00 0.30 0.00 — — — — — — — — — — — No. 16Specimen 0.00 1.00 0.00 Sm 2.00 0.30 0.00 — — — — — — — — — — — No. 17Specimen 0.00 1.00 0.00 Eu 2.00 0.30 0.00 — — — — — — — — — — — No. 18Specimen 0.00 1.00 0.00 Gd 2.00 0.30 0.00 — — — — — — — — — — — No. 19Specimen 0.00 1.00 0.00 Tb 2.00 0.30 0.00 — — — — — — — — — — — No. 20Specimen 0.00 1.00 0.00 Dy 2.00 0.30 0.00 — — — — — — — — — — — No. 21Specimen 0.00 1.00 0.00 Ho 2.00 0.30 0.00 — — — — — — — — — — — No. 22Specimen 0.00 1.00 0.00 Er 2.00 0.30 0.00 — — — — — — — — — — — No. 23Specimen 0.00 1.00 0.00 Tm 2.00 0.30 0.00 — — — — — — — — — — — No. 24Specimen 0.00 1.00 0.00 Yb 2.00 0.30 0.00 — — — — — — — — — — — No. 25Specimen 0.00 1.00 0.00 Lu 2.00 0.30 0.00 — — — — — — — — — — — No. 26Specimen 0.00 1.00 0.00 La, Sm 2.00 0.30 0.00 — — — — — — — — — — — No.27 ※Specimen 0.00 1.00 0.00 Bi 2.00 0.30 0.00 — — — — — — — — — — — No.28 ※Specimen 0.00 1.00 0.00 La 2.00 0.00 0.00 — — — — — — — — — — — No.29 ※Specimen 0.00 1.00 0.00 La 2.00 0.10 0.00 — — — — — — — — — — — No.30 Specimen 0.00 1.00 0.00 La 2.00 0.20 0.00 — — — — — — — — — — — No.31 Specimen 0.00 1.00 0.00 La 2.00 0.50 0.00 — — — — — — — — — — — No.32 Specimen 0.00 1.00 0.00 La 2.00 0.80 0.00 — — — — — — — — — — — No.33 Specimen 0.00 1.00 0.00 La 2.00 1.00 0.00 — — — — — — — — — — — No.34 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.05 — — — — — — — — — — — No.35 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.10 — — — — — — — — — — — No.36 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.50 — — — — — — — — — — — No.37 Specimen 0.00 1.00 0.00 La 2.00 0.30 1.00 — — — — — — — — — — — No.38 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.00 0.05 — — — — — — — — — —No. 39 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.00 0.10 — — — — — — — — —— No. 40 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.00 1.00 — — — — — — — —— — No. 41 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.00 10.00 — — — — — — —— — — No. 42 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.00 20.00 — — — — — —— — — — No. 43 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.00 30.00 — — — — —— — — — — No. 44 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.00 — 1.00 — — —— — — — — — No. 45 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.00 — — 1.00 —— — — — — — — No. 46 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.00 — — —1.00 — — — — — — — No. 47 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.00 — —— — 1.00 — — — — — — No. 48 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.00 —— — — — 1.00 — — — — — No. 49 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.00— — — — — — 1.00 — — — — No. 50 Specimen 0.00 1.00 0.00 La 2.00 0.300.00 — — — — — — — 1.00 — — — No. 51 Specimen 0.00 1.00 0.00 La 2.000.30 0.00 — — — — — — — — 1.00 — — No. 52 Specimen 0.00 1.00 0.00 La2.00 0.30 0.00 — — — — — — — — — 1.00 — No. 53 Specimen 0.00 1.00 0.00La 2.00 0.30 0.00 — — — — — — — — — — 1.00 No. 54 Specimen 0.00 1.000.00 La 2.00 0.30 0.00 — — — 3.00 — — 3.00 — — — — No. 55 Specimen 0.001.00 0.00 La 2.00 0.30 0.00 5.00 — 1.00 1.00 — 0.05 — — 10.00 — — No. 56※Specimen 0.00 1.00 0.00 La 2.00 0.00 1.00 10.00 — — — — — — — — — — No.57 Specimen 0.00 1.00 0.00 Pr 2.00 0.80 0.00 5.00 — — — — — — — — — —No. 58 Specimen 0.00 1.00 0.00 Nd 2.00 1.00 1.00 — — — — — — — — 5.00 —— No. 59 Specimen 0.20 0.50 0.30 Y 1.55 0.20 0.00 — — — — — — — — — — —No. 60 Specimen 0.20 0.50 0.30 Y 1.55 0.20 0.10 — — — — — — — — — — —No. 61 Specimen 0.20 0.50 0.30 Y 1.55 0.20 0.00 — — — — — 1.00 — — — — —No. 62 Specimen 0.00 1.00 0.00 La 2.00 0.30 0.00 — — — — — — — — — — —No. 63 Specimen 0.20 0.50 0.30 Y 1.55 0.20 0.00 — — — — — — — — — — —No. 64 Specimen 0.20 0.50 0.30 Y 1.55 0.20 0.10 — — — — — — — — — — —No. 65 ″—″ described in Table 1 indicates that a sub component is notcontained.

The dielectric composition raw material thus obtained (100 parts byweight), a polyvinyl butyral resin (10 parts by weight), dioctylphthalate (DOP) (5 parts by weight) as a plasticizer, and alcohol (100parts by weight) as a solvent were mixed with a ball mill to obtain apaste, thereby producing a paste for a dielectric layer.

Apart from the above, Pd particles (44.6 parts by weight), terpineol (52parts by weight), ethylcellulose (3 parts by weight), and benzotriazole(0.4 part by weight) were kneaded with a three-roll mill to obtain aslurry, thereby producing a paste for a Pd internal electrode layer. Inaddition, similarly to the paste for a Pd internal electrode layer, apaste for a Ni internal electrode layer was produced using Ni particles.

Then, a green sheet was formed using the produced paste for a dielectriclayer on a PET film to have a thickness after drying of 7 μm.Subsequently, an internal electrode layer was printed with apredetermined pattern using the paste for an internal electrode layer onthe green sheet, and then the sheet was peeled off from the PET film toproduce a green sheet having an internal electrode layer. Incidentally,the green sheets each having an internal electrode layer were producedwhile the paste for a Pd internal electrode layer was used in the greensheets using Specimen No. 1 to Specimen No. 62 and the paste for a Niinternal electrode layer was used in the green sheets using Specimen No.63 to Specimen No. 65. Subsequently, a plurality of green sheets havingan internal electrode layer were stacked and adhered by pressure toobtain a green multilayer body. This green multilayer body was cut in apredetermined size to obtain a green chip.

Then, regarding the obtained green chip, Specimen No. 1 to Specimen No.62 were subjected to a binder removal treatment in air (temperatureincrease rate: 10° C./hr, retention temperature: 400° C., temperatureretention time: 8 hours, atmosphere: in air) and subjected to firing inair (temperature increase rate: 200° C./hr, retention temperature: 1000to 1400° C., temperature retention time: 2 hours, cooling rate: 200°C./hr, atmosphere: in air), and Specimen No. 63 to Specimen No. 65 weresubjected to a binder removal treatment in nitrogen (temperatureincrease rate: 10° C./hr, retention temperature: 350° C., temperatureretention time: 8 hours, atmosphere: in nitrogen) and subjected tofiring in reductive atmosphere (temperature increase rate: 200° C./hr,retention temperature: 1000° C. to 1400° C., temperature retention time:2 hours, cooling rate: 200° C./hr, oxygen partial pressure: 10⁻⁹ to10⁻¹² Pa, atmosphere: H₂—N₂—H₂O mixed gas). Thus, capacitor element mainbodies were obtained.

The crystal structure of the dielectric layer of the obtained capacitorelement main body was subjected to X-ray diffraction (XRD) measurement,and as a result, it was confirmed that the tungsten bronze typecomposite oxide was obtained. In addition, the composition of thedielectric composition in the dielectric layer of the obtained capacitorelement main body was measured by inductively coupled plasma source massspectrometry (ICP-MS), and as a result, it was confirmed that thecomposition in Table 1 was obtained.

The end faces of the obtained capacitor element main body were polishedby sandblasting, and then an In—Ga eutectic alloy was applied as anexternal electrode to obtain multilayer ceramic capacitors of SpecimenNo. 1 to Specimen No. 65 having the same shape as the multilayer ceramiccapacitor illustrated in FIGURE. The sizes of the obtained multilayerceramic capacitors were all 3.2 mm×1.6 mm×1.2 mm, the thickness of thedielectric layer was set to 5.0 μm, the thickness of the internalelectrode layer was set to 1.5 μm, and the number of the dielectriclayers interposed between the internal electrode layers was set to 10.

The voltage resistance, the specific permittivity (cs), and the specificresistance of the obtained multilayer ceramic capacitors of Specimen No.1 to Specimen No. 65 were measured by the following methods andpresented in Table 2.

[Specific Permittivity (εs) and Dielectric Loss (tan δ)]

The capacitance C and the dielectric loss tan6 were measured for themultilayer ceramic capacitor at 25° C. and 200° C. by a digital LCRmeter (4284A manufactured by YHP) at a frequency of 1 kHz with a signal,which has an input signal level (measurement voltage) of 1 Vrms, beinginput. Then, the specific permittivity εs (no unit of quantity required)was calculated on the basis of the thickness of the dielectric layer,the effective electrode area, and the capacitance C obtained as a resultof the measurement. A higher specific permittivity was preferable andthe specific permittivity of 300 or more was determined to be favorable.A lower dielectric loss at 200° C. that is the usage temperatureenvironment to be assumed was preferable and the dielectric loss wasdetermined to be favorable when the dielectric loss was 0.5% or less,more preferably 0.30% or less, and further preferably 0.20% or less.

[Specific Resistance]

Insulation resistance was measured for the multilayer ceramic capacitorspecimen at 200° C. by a digital resistance meter (R8340 manufactured byADVANTEST CORPORATION) under conditions of a measurement voltage of 30 Vand a measurement time of 60 seconds. A value of specific resistance wascalculated from the electrode area of the capacitor specimen and thethickness of the dielectric layer. Higher specific resistance waspreferable, and the specific resistance was determined to be favorablewhen the specific resistance was 1.00×10¹² Ω/cm or more and morepreferably 9.00×10¹² Ωcm or more. When the specific resistance is low,leak current increases in the capacitor and malfunction occurs in anelectric circuit.

[Voltage Resistance]

A DC or AC voltage was applied to the multilayer ceramic capacitorspecimen at 200° C. at a pressure increase rate of 100 V/sec, and a casewhere leak current exceeds 10 mA was regarded as DC or AC voltageresistance. Higher DC voltage resistance was preferable, and the DCvoltage resistance was determined to be favorable when the DC voltageresistance was 150 V/μm or more, more preferably 160 V/μm or more, andfurther preferably 175 V/μm or more. In addition, higher AC voltageresistance was preferable, and the AC voltage resistance was determinedto be favorable when the AC voltage resistance was 45.0 V/μm or more,more preferably 50.0 V/μm or more, and further preferably 65.0 V/μm ormore.

TABLE 2 25° C. 25° C. 200° C. 200° C. 200° C. 200° C. SpecificDielectric Dielectric Specific AC voltage DC voltage permittivity lossloss resistance resistance resistance [−] [%] [%] [Ωcm] [V/μm] [V/μm]Specimen No. 1 338 0.47 0.39 7.73E+12 54.7 166 Specimen No. 2 335 0.620.39 7.78E+12 54.6 165 Specimen No. 3 325 0.83 0.37 7.75E+12 54.2 162Specimen No. 4 333 0.53 0.34 7.71E+12 54.3 161 Specimen No. 5 331 0.710.42 7.67E+12 53.3 162 ※Specimen No. 6 330 0.76 0.87 7.48E+12 36.1 156※Specimen No. 7 327 0.68 0.79 7.62E+12 36.9 162 ※Specimen No. 8 329 0.720.61 7.69E+12 43.1 162 ※Specimen No. 9 437 4.87 0.57 6.17E+12 42.8 165Specimen No. 10 356 1.21 0.42 6.56E+12 53.5 167 Specimen No. 11 339 0.470.38 7.63E+12 55.3 169 Specimen No. 12 325 0.44 0.36 7.59E+12 55.8 168※Specimen No. 13 — — — — — — Specimen No. 14 336 1.38 0.35 7.69E+12 54.6165 Specimen No. 15 335 1.23 0.38 7.75E+12 54.2 164 Specimen No. 16 3371.67 0.35 7.67E+12 54.5 166 Specimen No. 17 340 1.93 0.36 7.65E+12 54.4164 Specimen No. 18 338 1.98 0.33 7.60E+12 54.4 165 Specimen No. 19 3442.18 0.35 7.70E+12 54.6 166 Specimen No. 20 337 2.11 0.32 7.67E+12 54.3164 Specimen No. 21 335 1.96 0.34 7.62E+12 54.5 167 Specimen No. 22 3362.03 0.31 7.61E+12 54.2 163 Specimen No. 23 338 2.05 0.34 7.68E+12 54.1165 Specimen No. 24 335 2.05 0.33 7.64E+12 53.9 162 Specimen No. 25 3402.08 0.31 7.59E+12 54.2 166 Specimen No. 26 337 2.14 0.32 7.58E+12 54.0165 Specimen No. 27 340 0.86 0.34 7.71E+12 54.5 167 ※Specimen No. 28 3362.13 0.39 7.62E+12 52.8 129 ※Specimen No. 29 346 0.52 0.46 5.45E+11 42.1136 ※Specimen No. 30 344 0.51 0.44 3.18E+12 43.7 162 Specimen No. 31 3410.47 0.37 4.23E+12 52.3 164 Specimen No. 32 335 0.42 0.28 8.09E+12 66.2176 Specimen No. 33 329 0.41 0.27 9.58E+12 66.4 177 Specimen No. 34 3270.37 0.27 1.54E+13 66.5 179 Specimen No. 35 333 0.45 0.28 7.79E+12 65.7165 Specimen No. 36 328 0.43 0.25 8.01E+12 66.2 171 Specimen No. 37 3140.34 0.24 8.15E+12 66.5 173 Specimen No. 38 309 0.25 0.24 9.09E+12 66.7174 Specimen No. 39 339 0.27 0.26 8.13E+12 57.3 169 Specimen No. 40 3360.18 0.16 9.35E+12 65.6 177 Specimen No. 41 337 0.17 0.15 9.63E+12 66.2185 Specimen No. 42 334 0.18 0.15 9.47E+12 65.9 184 Specimen No. 43 3290.16 0.17 9.45E+12 65.9 183 Specimen No. 44 328 0.23 0.25 8.59E+12 58.0170 Specimen No. 45 336 0.19 0.15 9.29E+12 65.6 183 Specimen No. 46 3350.21 0.17 9.05E+12 65.9 184 Specimen No. 47 337 0.18 0.16 9.22E+12 65.7182 Specimen No. 48 333 0.17 0.16 9.17E+12 65.7 181 Specimen No. 49 3340.20 0.15 9.19E+12 65.8 182 Specimen No. 50 339 0.18 0.17 9.43E+12 66.1186 Specimen No. 51 332 0.24 0.18 9.38E+12 65.7 184 Specimen No. 52 3410.19 0.17 9.51E+12 66.0 188 Specimen No. 53 330 0.17 0.15 9.46E+12 66.2187 Specimen No. 54 334 0.45 0.27 5.47E+12 55.3 167 Specimen No. 55 3350.17 0.16 9.22E+12 66.1 185 Specimen No. 56 336 0.17 0.18 9.49E+12 65.8187 ※Specimen No. 57 316 0.31 0.42 5.27E+11 42.5 128 Specimen No. 58 3350.61 0.09 1.65E+13 68.4 203 Specimen No. 59 307 0.72 0.07 1.86E+13 68.6209 Specimen No. 60 348 1.31 0.39 2.72E+12 47.6 152 Specimen No. 61 3411.26 0.27 3.16E+12 53.1 164 Specimen No. 62 347 0.65 0.18 9.48E+12 65.3177 Specimen No. 63 336 0.48 0.38 7.37E+12 54.2 169 Specimen No. 64 3391.35 0.39 1.58E+12 47.3 151 Specimen No. 65 344 1.25 0.25 2.79E+12 53.2166 ″—″ described in Table 2 indicates ″unmeasurable.″

As presented in Table 2, the multilayer ceramic capacitor specimens inwhich the amounts s and t, and 1.00−(s+t) of Ba, Ca, and Sr as the maincomponents are respectively 0.50≤s≤1.00, 0.00≤t≤0.30, and 0.50≤s+t≤1.00have high DC voltage resistance and high AC voltage resistance at 200°C.

As presented in Table 2, the multilayer ceramic capacitor specimens inwhich the substitution amount x of R as the main component is1.50<x≤3.00 have a low dielectric loss at 200° C. of 0.5% or less andhigh AC voltage resistance at 200° C. In the case of Specimen No. 13 inwhich x>3.00 is satisfied, the main component is difficult tosynthesize.

As presented in Table 2, the multilayer ceramic capacitor specimens inwhich R as the main component is at least one element selected from Y,La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu have high DCvoltage resistance and high AC voltage resistance at 200° C.

As presented in Table 2, the multilayer ceramic capacitor specimens inwhich the substitution amount a of Zr as the main component is0.20≤a≤1.00 have high DC voltage resistance and high AC voltageresistance at 200° C. Of these, in the case of the multilayer ceramiccapacitor specimens in which 0.50≤a≤1.00 is satisfied, the DC voltageresistance at 200° C. becomes higher. Specimen No. 29 in which a=0 issatisfied has low specific resistance at 200° C. and low DC voltageresistance at 200° C.

As presented in Table 2, also in Specimen No. 35 to Specimen No. 38 inwhich Nb as the main component is substituted with Ta, the DC voltageresistance and the AC voltage resistance at 200° C. are high, and in thecase of Specimen No. 36 to Specimen No. 38 in which the substitutionamount b of Ta is set to 0.10≤b≤1.00, the DC voltage resistance and theAC voltage resistance at 200° C. are higher.

As presented in Table 2, the multilayer ceramic capacitor specimens inwhich the molar quantity of the sub component with respect to 100 mol ofthe main component is 0.10 mol≤the sub component≤20.00 mol have higherspecific resistance at 200° C.

As presented in Table 2, the multilayer ceramic capacitor specimens inwhich at least one selected from Mn, Mg, Co, V, W, Mo, Si, Li, B, and Alis contained as a sub component have higher specific resistance at 200°C.

Also in Specimen No. 63 to Specimen No. 65 produced using a Ni internalelectrode by reductive atmosphere firing, it is possible to confirm thatthe specific resistance, the DC voltage resistance, and the AC voltageresistance at 200° C. exhibit high values.

Comparative Example

In Specimen No. 66 and Specimen No. 67 presented in Table 3, multilayerceramic capacitors were produced using a tungsten bronze type compositeoxide containing an alkali metal element as a main component. Thespecific manufacturing method will be described below. Incidentally, aspecimen marked with × in Table 3 is a comparative example.

In Specimen No. 66 and Specimen No. 67, tungsten bronze type compositeoxide K(Sr_(0.3)Ba_(0.3)Ca_(.04))₂Nb₅O₁₅ powder containing an alkalimetal element synthesized in advance was prepared as a main component,and MnCO₃ powder that is a raw material of a sub component to be addedto the main component was prepared. Then,K(Sr_(0.3)Ba_(0.3)Ca_(0.4))₂Nb₅O₁₅ powder as the main component andMnCO₃ powder as the raw material of the sub component were weighed andmixed to have a predetermined ratio of the sub component to 100 mol ofthe main component, thereby preparing mixed powder.

The mixed powder of the main component and the sub component is used asa dielectric composition raw material.

A paste for a dielectric layer was produced in the similar manner to theexample, except that the dielectric composition raw material was used,and a green sheet was formed on a PET film to have a thickness afterdrying of 7 μm. Then, an internal electrode layer was printed with apredetermined pattern on the green sheet using a paste for an internalelectrode containing Ni as a main component, and then the sheet waspeeled off from the PET film to produce a green sheet having an internalelectrode layer. Subsequently, a green chip was obtained using the greensheet similarly to the example.

Then, the obtained green chip was subjected to a binder removaltreatment (temperature increase rate: 10° C./hr, retention temperature:350° C., temperature retention time: 8 hours, atmosphere: in nitrogen)and subjected to firing (temperature increase rate: 200° C./hr,retention temperature: 1100° C., temperature retention time: 2 hours,cooling rate: 200° C./hr, oxygen partial pressure: 10⁻⁹ to 10⁻¹² Pa,atmosphere: H₂—N₂—H₂O mixed gas) to obtain a capacitor element mainbody.

Both end faces of the obtained capacitor element main body were appliedwith a Ag paste containing B₂O₃—SiO₂—BaO-based glass frit and subjectedto a baking treatment (temperature: 800° C., atmosphere: N₂ gas) toobtain multilayer ceramic capacitors having the same shape as themultilayer ceramic capacitor illustrated in FIGURE. The sizes of theobtained multilayer ceramic capacitors were all 4.5 mm×3.2 mm×0.5 mm,the thickness of the dielectric layer was set to 6.0 μm, the thicknessof the internal electrode layer was set to 1.5 μm, and the number of thedielectric layers interposed between the internal electrode layers wasset to 5.

As for the obtained multilayer ceramic capacitors of Specimen No. 66 andSpecimen No. 67, similarly to the example, the specific permittivity,the dielectric loss, the specific resistance, the DC voltage resistance,and the AC voltage resistance were measured and the results thereof werepresented in Table 3.

TABLE 3 Accessory component [mol %] 200° C. 200° C. (with respect to 25°C. 25° C. 200° C. 200° C. AC DC 100 mol of main Specific DielectricDielectric Specific voltage voltage Main component component)permittivity loss loss resistance resistance resistance composition Mn[−] [%] [%] [Ωcm] [V/μm] [V/μm] ※SpecimenK(Sr_(0.3)Ba_(0.3)Ca_(0.4))₂Nb₅O₁₅ 40.00 1900 7.0 2.9 1.51E+09 42.2 134No. 66 ※Specimen K(Sr_(0.3)Ba_(0.3)Ca_(0.4))₂Nb₅O₁₅ 5.00 1900 6.0 2.79.56E+08 42.0 133 No. 67

As presented in Table 3, it is possible to confirm that Specimen No. 66and Specimen No. 67 that are a tungsten bronze type composite oxidecontaining an alkali metal element as a main component have low valuesof the voltage resistance and the specific resistance, and have a highvalue of the dielectric loss at 25° C., since a lattice defect caused bythe alkali metal element with high volatility easily occurs and theconduction electron is easily generated.

INDUSTRIAL APPLICABILITY

The dielectric composition of the present invention can be applied underthe environment close to an engine room as an in-vehicle electroniccomponent since the dielectric composition has high DC voltageresistance, high AC voltage resistance, high specific resistance, and alow dielectric loss in a high-temperature region of 200° C., and can bealso applied to use application as an electronic component mounted inthe vicinity of a power device using a SiC- or GaN-based semiconductor.

EXPLANATIONS OF LETTERS OR NUMERALS

1 MULTILAYER CERAMIC CAPACITOR

2 DIELECTRIC LAYER

3 INTERNAL ELECTRODE LAYER

4 EXTERNAL ELECTRODE

10 CAPACITOR ELEMENT MAIN BODY

The invention claimed is:
 1. A dielectric composition comprising, as amain component, a tungsten bronze type composite oxide represented by achemical formula((Sr_(1.00-(s+t))Ba_(s)Ca_(t))_(6.00−x)R_(x)(Ti_(1.00-a)Zr_(a))_(x+2.00)(Nb_(1.00−b)Ta_(b))_(8.00−x)O_(30.00), wherein the R is at least one element selected from Y, La, Pr, Nd, Sm,Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, and s, t, x, a, and b satisfy0.50≤s≤1.00, 0≤t≤0.30, 0.50≤s+t≤1.00, 1.50<x≤3.00, 0.20≤a≤1.00, and0≤b≤1.00.
 2. The dielectric composition according to claim 1, wherein atleast one selected from Mn, Mg, Co, V, W, Mo, Si, Li, B, and Al iscontained as a sub component in 0.10 mol or more and 20.00 mol or lesswith respect to 100 mol of the main component.
 3. The dielectriccomposition according to claim 1, wherein a substitution amount a of Zrin the chemical formula is 0.50≤a≤1.00.
 4. A dielectric elementcomprising the dielectric composition according to claim
 1. 5. Anelectronic component comprising a dielectric layer comprising thedielectric composition according to claim
 1. 6. A multilayer electroniccomponent comprising a multilayer portion wherein a dielectric layercomprising the dielectric composition according to claim 1 and aninternal electrode layer alternately stacked.